Polymerizable liquid crystal composition and uses for the same

ABSTRACT

The polymerizable liquid crystal composition includes at least two selected from the group of compounds represented by the following Formulas (1) and (2): 
                         
wherein m is 5 or 10; and
 
                         
wherein n is 3, 4, 6, 7, 8 or 9, and R is hydrogen or methyl
     wherein said composition includes at most only two compounds of Formula (1) in which m is 10; and   wherein said composition does not include a compound of Formula (2) in which n is 3 and R is hydrogen.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 11/819,663,filed on Jun. 28, 2007, the entire contents of which are incorporatedherein by reference. This application also claims priority under 35U.S.C. §119 to Japanese Patent Application Nos. JP 2006-180389 (filedJun. 29, 2006) and JP 2007-130971 (filed May 16, 2007), whichapplications are expressly incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a polymerizable liquid crystal composition anduses for the same, more specifically to a polymerizable liquid crystalcomposition which reflects light of a specific wavelength in thevicinity of room temperature, a polymer including the above compositionand uses for the above polymer.

2. Related Art

A cholesteric liquid crystal molecule has a spiral structure in a liquidcrystal state. Accordingly, when a cholesteric liquid crystal phase isirradiated with light, it reflects a circular polarizing light of aspecific wavelength corresponding to a spiral rotational direction ofthe liquid crystal molecule and a length of the pitch. For example, whenirradiated with a visible light, it reflects selectively lights havingwavelengths of blue, green, yellow and red corresponding to a length ofa pitch in the liquid crystal. The color tones thereof are differentfrom those of pigments and dyes which take on colors by absorption oflights and have a visual dependency in which a color tone changesaccording to viewing angles. Further, a length of a pitch in cholestericliquid crystal can be controlled by temperature and the kind ofcompounds, and therefore it can selectively reflect not only visiblelights but also lights of near infrared and ultraviolet regions.

There have been materials which selectively reflect lights of variouswavelengths in a broad wavelength region making use of thecharacteristics of the cholesteric liquid crystal. They are, forexample, liquid crystal pigments, coating materials, spray inks, printinks, cosmetics, printed matters for preventing counterfeit, ornamentalarticles and the like. Further, they are proposed as well for polarizingplates in optical devices such as liquid crystal displays andholographic devices, compensation plates, optical films such as colorfilters and the like. In the case of a cholesteric liquid crystalpigment which is an existing material, flake-shaped cholesteric liquidcrystal polymers and microencapsulated cholesteric liquid crystal areused. The uses thereof include coating materials for cars, cosmeticingredients and the like.

A polymer of a mixture including a chiral polymerizable mesogen compoundhaving an optically active group, a non-chiral polymerizable mesogencompound, a photoinitiator and the like is described as a pigment whichis processed in a flake form in JP 2000-505485 T (Patent Document 1; WO97/30136). In Patent Document 1, the kind of chiral polymerizablemesogen compound and the content thereof in the mixture are changed tothereby control the pitch in a spiral of cholesteric liquid crystal andobtain a pigment having a desired color tone.

Further, a microencapsulated liquid crystal material is described in JPH8-24625 A/1996 (Patent Document 2). The above material has a structurein which a copolymer of glutamic γ-ester having a thermotropiccholesteric liquid crystallinity is covered with a film including anepoxy resin and amine as structural components. The glutamic γ-estercopolymer has a high cohesive property and therefore has to be alignedby applying a shearing stress after being molten in order to solidifyit. In Patent Document 2, however, cohesion can be avoided bymicroencapsulation, and the operability in solidification is enhanced.

The above flake-shaped or microencapsulated liquid crystal material isused as a color material for coating materials, ink components andcosmetic ingredients. However, a flake-shaped pigment used as a colormaterial is produced by forming a cholesteric polymer layer on asupport, peeling it and then crushing the polymer layer. A microcapsuleis produced by forming a resin coating film on a cholesteric liquidcrystal material. Further, a process of a multistage in which they aredispersed once in a solvent, coated on an object material and fixed isrequired.

In contrast with this, in JP H10-508882 T/1998 (Patent Document 3; U.S.Pat. No. 5,798,147), a composition including a polymerizable liquidcrystal monomer and a chiral liquid crystal monomer or a chiralnon-liquid crystal monomer is applied directly or after being dissolvedin a solvent on a support at a relatively low temperature, and it isthen cured by an energy beam. In Patent Document 3, a compositionincluding a mixture of tricyclic liquid crystalline compounds in which anematic phase area is 90° C. or higher and a chiral monomer is used inexamples. Further, in mixing the respective components of thecomposition, they are dissolved in dichloromethane and then subjectedonce to heat treatment up to 70° C. A cholesteric material which is acolor material preferably exhibits a stable cholesteric liquid crystalphase in the vicinity of room temperature in order to carry out coatingand print treatment in the vicinity of room temperature of a relativelylow temperature.

A composition including 2 to 3 components of polymerizable liquidcrystal monomers which are cholesterol derivatives is described as theabove material in JP S59-109505 A/1984 (Patent Document 4; U.S. Pat. No.4,637,896). Among them, a 1:1 mixture of a compound Va and a compound Veeach described in Example 7 exhibits a cholesteric phase in a widetemperature range and realizes fixation of cholesteric colors of blue,green and orange by photocuring in a range of 10 to 32° C. in thevicinity of room temperature. In the method of the Patent Document 4,however, the temperature of the materials has to be controlled at aninterval of 5° C. in curing in order to obtain the targeted polymer, anda polymer which takes on specific reflected colors of red, green andblue at a fixed room temperature has not been obtained.

SUMMARY OF THE INVENTION

The invention relates to a polymerizable liquid crystal compositionincluding at least two selected from the group of compounds representedby Formulas (1) and (2):

wherein m is 5 or 10; and

wherein n is 3, 4, 6, 7, 8 or 9, and R is hydrogen or methyl;

-   wherein said composition includes at most two compounds of    Formula (1) in which m is 10; and-   wherein said composition does not include a compound of Formula (2)    in which n is 3 and R is hydrogen.

DETAILED DESCRIPTION OF THE INVENTION

The first object of the invention is to provide a polymerizable liquidcrystal composition showing a cholesteric phase in the vicinity of roomtemperature. The second object of the invention is to control areflected color in a cholesteric reflection zone over a wide range ofred, green, blue and purple by changing the constitution of thecomposition. The third object thereof is to form and fix a coating filmexhibiting a cholesteric liquid crystal phase directly on a substratewhich is an object of cholesteric liquid crystal.

It has been observed that the problems described above can be solved byapplying a composition including two or more kinds of specificpolymerizable liquid crystal compounds on the surface of a substratewhich is an object and curing it by heat and/or light. The inventionincludes:

[1] A polymerizable liquid crystal composition including at least twoselected from the group of compounds represented by Formulas (1) and(2):

wherein m is 5 or 10; and

wherein n is 3, 4, 6, 7, 8 or 9, and R is hydrogen or methyl;

-   wherein said composition includes at most two compounds of    Formula (1) in which m is 10; and-   wherein said composition does not include a compound of Formula (2)    in which n is 3 and R is hydrogen.

[2] The polymerizable liquid crystal composition as described in item[1], further including at least one compound selected from the group ofcompounds represented by Formulas (3), (4) and (10):

wherein p is 5 or 10;

wherein q is 2, 4 or 6, and R is hydrogen or methyl; and

wherein t is 2, 3 or 4, and R is hydrogen or methyl.

[3] The polymerizable liquid crystal composition as described in item[1], including the compound in which m is 5 in Formula (1) and thecompound in which n is 3 and R is hydrogen in Formula (2).

[4] The polymerizable liquid crystal composition as described in item[1], including the compound in which m is 5 in Formula (1), the compoundin which m is 10 in Formula (1) and the compound in which n is 3 and Ris hydrogen in Formula (2).

[5] The polymerizable liquid crystal composition as described in item[1], including the compound in which m is 5 in Formula (1) and thecompound in which n is 4 and R is hydrogen in Formula (2).

[6] The polymerizable liquid crystal composition as described in item[1], including the compound in which m is 5 in Formula (1) and thecompound in which m is 10 in Formula (1).

[7] The polymerizable liquid crystal composition as described in item[2], including the compound in which m is 5 in Formula (1), the compoundin which n is 3 and R is hydrogen in Formula (2) and the compound inwhich q is 2 and R is hydrogen in Formula (4).

[8] The polymerizable liquid crystal composition as described in item[2], including the compound in which m is 5 in Formula (1), the compoundin which m is 10 in Formula (1) and the compound in which q is 2 and Ris methyl in Formula (4).

[9] The polymerizable liquid crystal composition as described in item[2], including the compound in which m is 5 in Formula (1), the compoundin which n is 3 in Formula (2) and the compound in which t is 2 inFormula (10).

[10] The polymerizable liquid crystal composition as described in item[2], including the compound in which m is 5 in Formula (1), the compoundin which n is 3 in Formula (2) and the compound in which t is 3 inFormula (10).

[11] The polymerizable liquid crystal composition as described in item[2], including the compound in which m is 5 in Formula (1), the compoundin which n is 3 in Formula (2) and the compound in which t is 4 inFormula (10).

[12] A polymerizable liquid crystal composition including at least oneselected from the group of compounds represented by Formula (5) and atleast one selected from the group of compounds represented by Formula(6):

wherein r is an integer of 3 to 9, and R is hydrogen or methyl; and

wherein q is 2, 4 or 6.

[13] The polymerizable liquid crystal composition as described in item[12], further including at least one selected from the group ofcompounds represented by Formula (10):

wherein t is 2, 3 or 4, and R is hydrogen or methyl.

[14] The polymerizable liquid crystal composition as described in item[13], including the compound in which r is 5 in Formula (5), thecompound in which q is 2 in Formula (6) and the compound in which t is 2in Formula (10).

[15] The polymerizable liquid crystal composition as described in item[13], including the compound in which r is 5 in Formula (5), thecompound in which q is 4 in Formula (6) and the compound in which t is 2in Formula (10).

[16] The polymerizable liquid crystal composition as described in item[13], including the compound in which r is 5 in Formula (5), thecompound in which q is 2 in Formula (6) and the compound in which t is 3in Formula (10).

[17] The polymerizable liquid crystal composition as described in theitem [13], including the compound in which r is 5 in Formula (5), thecompound in which q is 4 in Formula (6) and the compound in which t is 3in Formula (10).

[18] The polymerizable liquid crystal composition as described in item[12], further including at least one selected from the group ofcompounds represented by Formulas (7) and (8):

wherein R is hydrogen or methyl; and

wherein q is 2, 4 or 6.

[19] The polymerizable liquid crystal composition as described in theabove item [12], including the compound in which r is 5 and R ishydrogen in Formula (5) and the compound in which q is 2 in Formula (6).

[20] A polymerizable liquid crystal composition including at least oneselected from the group of compounds represented by Formula (9), atleast one selected from the group of compounds represented by Formula(8) and at least one selected from the group of multifunctional(meth)acryl monomers and (meth)acryl oligomers:

wherein s is an integer of 3 to 10, and R is hydrogen or methyl; and

wherein q is 2, 4 or 6.

[21] A polymerizable liquid crystal composition including at least oneselected from the group of compounds represented by Formula (5) and atleast one selected from the group of compounds represented by Formula(10):

wherein r is an integer of 3 to 9, and R is hydrogen or methyl; and

wherein t is 2, 3 or 4, and R is hydrogen or methyl.

[22] The polymerizable liquid crystal composition as described in item[21], including the compound in which r is 3 in Formula (5) and thecompound in which t is 3 in Formula (10).

[23] The polymerizable liquid crystal composition as described in item[21], including the compound in which r is 5 in Formula (5) and thecompound in which t is 2 in Formula (10).

[24] The polymerizable liquid crystal composition as described in item[21], including the compound in which r is 5 in Formula (5) and thecompound in which t is 3 in Formula (10).

[25] The polymerizable liquid crystal composition as described in item[21], including the compound in which r is 5 in Formula (5) and thecompound in which t is 4 in Formula (10).

[26] The polymerizable liquid crystal composition as described in item[21], further including at least one selected from the group ofcompounds represented by Formula (4):

wherein q is 2, 4 or 6, and R is hydrogen or methyl.

[27] The polymerizable liquid crystal composition as described in item[26], including the compound in which r is 3 in Formula (5), thecompound in which t is 3 in Formula (10) and the compound in which q is4 in Formula (4).

[28] The polymerizable liquid crystal composition as described in item[26], including the compound in which r is 5 in Formula (5), thecompound in which t is 3 in Formula (10) and the compound in which q is2 in Formula (4).

[29] A polymerizable liquid crystal composition including at least oneselected from the group of compounds represented by Formula (4) and atleast one selected from the group of compounds represented by Formula(10):

wherein q is 2, 4 or 6, and R is hydrogen or methyl; and

wherein t is 2, 3 or 4, and R is hydrogen or methyl.

[30] The polymerizable liquid crystal composition as described in item[29], including the compound in which q is 2 in Formula (4) and thecompound in which t is 2 in Formula (10).

[31] The polymerizable liquid crystal composition as described in theabove item [29], including the compound in which q is 2 in Formula (4)and the compound in which t is 3 in Formula (10).

[32] The polymerizable liquid crystal composition as described in item[29], including the compound in which q is 4 in Formula (4) and thecompound in which t is 2 in Formula (10).

[33] The polymerizable liquid crystal composition as described in item[29], including the compound in which q is 4 in Formula (4) and thecompound in which t is 3 in Formula (10).

[34] The polymerizable liquid crystal composition as described in any ofitems [1] to [19] and [21] to [33], further including a non-liquidcrystalline polymerizable compound.

[35] The polymerizable liquid crystal composition as described in item[34], wherein the non-liquid crystalline polymerizable compound is atleast one selected from the group of monofunctional (meth)acrylmonomers, multifunctional (meth)acryl monomers and (meth)acryloligomers.

[36] A cosmetic ingredient including the polymerizable liquid crystalcomposition as described in any of items [1] to [35].

[37] A printing ink including the polymerizable liquid crystalcomposition as described in any of items [1] to [35].

[38] A UV curing type printing ink including the polymerizable liquidcrystal composition as described in any of items [1] to [35].

[39] A polymer obtained by polymerizing the polymerizable liquid crystalcomposition as described in any of items [1] to [35].

[40] The polymer as described in the above item [39], exhibiting acholesteric liquid crystal phase.

[41] A membrane including the polymer as described in items [39] or[40].

[42] A film including the polymer as described in items [39] or [40].

[43] A cosmetic ingredient including the polymer as described in items[39] or [40].

[44] A color material including the polymer as described in items [39]or [40].

[45] Use of the polymer as described in items [39] or [40] forapplications selected from liquid crystal pigments, coating materials,spray inks, print inks, cosmetics, printed matters for preventingcounterfeit, ornamental articles, toys and optical films.

According to the invention, a polymerizable liquid crystal compositionis obtained which exhibits a cholesteric phase in the vicinity of roomtemperature and can control a reflected color in a cholestericreflection zone over a wide range of red, green, blue and purple bychanging the composition, and which can be applied directly on an objectmatter to form and fix a coating film. Accordingly, a multistageoperation in which a cholesteric polymer which is a polymerized matteris crushed to a flake form and in which cholesteric liquid crystal ismicroencapsulated, mixed again with a solvent and applied is notrequired.

The polymerizable liquid crystal composition according to the invention,a polymer made from the composition and uses thereof shall be explainedbelow in details. As used herein, the polymerizable liquid crystalcompound represented by Formula (1) shall be referred to as the“compound (1),” and the compounds represented by the other formulasshall be referred to in the same abbreviation. The meaning of “liquidcrystalline” shall not be restricted only to having a liquid crystalphase, and the characteristic that a compound itself does not have aliquid crystal phase but can be used as a component for a liquid crystalcomposition when mixed with other liquid crystal compounds is includedas well in the meaning of “liquid crystalline.”

Polymerizable Liquid Crystal Composition

The polymerizable liquid crystal composition according to the inventionincludes: as the first embodiment, a composition including at least twomonofunctional liquid crystalline acrylate compounds selected from thegroup of the compound (1) and the compound (2) as essential components(hereinafter referred to as the “composition (I)”); as the secondembodiment, a composition including at least one compound selected fromthe compounds (5) and at least one selected from the compounds (6)(hereinafter referred to as the “composition (II)”); as the thirdembodiment, a composition including at least one compound selected fromthe compounds (9), at least one compound selected from the compounds (8)and at least one compound selected from the group of multifunctional(meth)acrylates and (meth)acryl oligomers (hereinafter referred to asthe “composition (III)”); as the fourth embodiment, a compositionincluding at least one s compound elected from the compounds (5) and atleast one compound selected from the compounds (10) (hereinafterreferred to as the “composition (IV)”); and as the fifth embodiment, acomposition including at least one compound selected from the compounds(4) and at least one compound selected from the compounds (10)(hereinafter referred to as the “composition (V)”). The polymerizableliquid crystal composition of the invention has a broad cholestericliquid crystal phase in the vicinity of room temperature (about 10 to40° C.), and a wavelength region of light reflected by the cholestericphase can be controlled by changing the composition ratios of therespective structural components and the temperature in curing thecomposition, which make it possible to form a polymer reflecting lightof a wavelength according to the desired colors and the purposes.

Composition (I)

The composition (I) of the invention includes as essential components,at least two monofunctional liquid crystalline acrylate compoundsselected from the group of the compound (1) and the compound (2).However, excluded is a combination including only two kinds of acompound in which m is 10 in Formula (1) described above and a compoundin which n is 3 and R is hydrogen in Formula (2) described above.Accordingly, combination including of a compound in which m is 10 inFormula (1) described above, a compound in which n is 3 and R ishydrogen in Formula (2) described above and at least one anothercompound (for example, a compound in which m is 5 in Formula (1)described above) selected from the compounds (1) and (2) belongs to thecomposition (I) of the invention.

The composition (I) of the invention may further include at least onecompound selected from the group of the compound (3), the compound (4)and the compound (10) in addition to the compounds (1) and (2). Further,the composition (I) of the invention may include a polymerizablecompound (hereinafter referred to as the “other polymerizable compound”)other than the compounds (1) to (4), a non-polymerizable component, anorganic solvent and the like.

A preferred embodiment of the composition (I) of the invention includes,for example: the combination of the compound in which m is 5 in Formula(1) and the compound in which n is 3 and R is hydrogen in Formula (2);the combination of the compound in which m is 5 in Formula (1), thecompound in which m is 10 in Formula (1) and the compound in which n is3 and R is hydrogen in Formula (2); the combination of the compound inwhich m is 5 in Formula (1) and the compound in which n is 4 and R ishydrogen in Formula (2); the combination of the compound in which m is 5in Formula (1) and the compound in which m is 10 in Formula (1); thecombination of the compound in which m is 5 in Formula (1), the compoundin which n is 3 and R is hydrogen in Formula (2) and the compound inwhich q is 2 and R is hydrogen in Formula (4); the combination of thecompound in which m is 5 in Formula (1), the compound in which m is 10in Formula (1) and the compound in which q is 2 and R is methyl inFormula (4); the combination of the compound in which m is 5 in Formula(1), the compound in which n is 3 in Formula (2) and the compound inwhich t is 2 in Formula (10); the combination of the compound in which mis 5 in Formula (1), the compound in which n is 3 in Formula (2) and thecompound in which t is 3 in Formula (10); and the combination of thecompound in which m is 5 in Formula (1), the compound in which n is 3 inFormula (2) and the compound in which t is 4 in Formula (10).

In respect to the characteristics of the compounds (1) and (2) beforepolymerization, both are compounds having an optical activity and havelarge HTP (helical twist power) and a good compatibility with otherpolymerizable liquid crystal compounds, compositions and solvents, andthey can develop spiral pitches according to purposes. The compound (1)exhibits a cholesteric liquid crystal phase in the vicinity of roomtemperature and shows alone a reflected color including mainly green toblue (purple) colors. The compound (2) is liable to be crystallizedalone in the vicinity of room temperature.

In the composition (I) of the invention, at least two compounds selectedfrom the compounds (1) and (2) as essential components are mixed, andthe combination of the structural components, the composition ratiothereof or the temperature in curing is changed, whereby a compositionis obtained exhibiting a cholesteric phase in a relatively broadtemperature area in the vicinity of room temperature.

The contents of the respective components selected from the compounds(1) and (2) in the composition (I) of the invention are usuallyapproximately 2 weight % or more, preferably approximately 5 weight % ormore respectively based on approximately 100 weight % of the total ofthe essential components.

When the composition (I) of the invention contains each at least one ofthe compounds (1) and the compounds (2), a content of the compound (1)is preferably approximately 40 to approximately 98 weight %, morepreferably approximately 50 to approximately 95 weight %, and a contentof the compound (2) is preferably approximately 2 to approximately 60weight %, more preferably approximately 5 to approximately 50 weight %each based on approximately 100 weight % of the total of the essentialcomponents.

The compounds (1) and (2) can be synthesized, for example, by thefollowing synthetic schemes.

In the synthetic scheme described above, a carboxylic acid derivative[a] having a hydroxy group can be synthesized by a hydrolytic method oflactones described in examples of GB2070596B2 or hydrolysis ofhalogenated aliphatic carboxylic acid derivatives described inGB2085881A. Also, a carboxylic acid derivative [b] having —OCOCH═CH₂ canbe synthesized according to a method described in Tetrahedron 60 (51),11765 to 11770, (2004). A production method of a derivative [d] ofcholesterol ester which is a final product is disclosed in Journal ofFluorine Chemistry 109 (2), 205 to 208, (2001).

The synthetic scheme described above shall be explained by showing anexample thereof. The compound [a] is obtained by hydrolyzing lactonessuch as γ-butyrolactone and ε-caprolactone or halogenated fatty acidssuch as 11-bromoundecanoic acid in an alkaline aqueous solution. Thecompound [a] obtained is acrylated to obtain the compound [b], and thenthe compound [b] is subjected to esterification reaction withcholesterol [c], whereby the compound [d] which corresponds to thecompound (1) and the like can be synthesized.

The compounds (3), (4) and (10) are optically active compounds as is thecase with the compounds (1) and (2), and they have large HTP (helicaltwist power).

At least one compound selected from the compounds (3), (4) and (10)which is contained in the composition (I) of the invention makes itpossible to prevent the composition from being crystallized at roomtemperature, control a reflected color at a specific temperature anddevelop a cholesteric phase showing reflected colors of red, orange,green and blue (purple) in a broader temperature region. Specifically,the compound (10) has a high effect in terms of preventing thecomposition from being crystallized at room temperature.

In the composition (I) of the invention, a content of the componentselected from the compounds (3), (4) and (10) is preferablyapproximately 5 to approximately 60 weight %, more preferablyapproximately 10 to approximately 50 weight % based on approximately 100weight % of the total of the compounds (1) to (4) and (10).

The compound (3) can be synthesized by the same method as in thecompounds (1) and (2). Further, the compound (4) can be synthesizedaccording to the following synthetic scheme.

As shown in the synthetic scheme described above, a carbonate derivative[g] can be synthesized by reacting 2-(chlorocarbonyloxy)alkyl acrylate[e] with cholesterol [f].

The compound (10) can be synthesized according to the followingsynthetic scheme.

As shown in the synthetic scheme described above, a carbonate derivative[j] can be synthesized by reacting 2-(chlorocarbonyloxy)alkyl etheracrylate [h] with cholesterol [i].

Composition (II)

The composition (II) of the invention includes at least one compoundselected from compounds (5) and at least one compound selected fromcompounds (6). The composition (II) of the invention may further includeat least one compound selected from the group of the compound (10) or atleast one compound selected from the group of the compound (7) and thecompound (8) in addition to the compounds (5) and (6). Further, thecomposition (II) of the invention may include a polymerizable compound(the other polymerizable compound) other than the compounds (5) to (8)and (10), a non-polymerizable component, an organic solvent and thelike.

The preferred embodiment of the composition (II) of the inventionincludes, for example, the combination of the compound in which r is 5in Formula (5), the compound in which q is 2 in Formula (6) and thecompound in which t is 2 in Formula (10); the combination of thecompound in which r is 5 in Formula (5), the compound in which q is 4 inFormula (6) and the compound in which t is 2 in Formula (10); thecombination of the compound in which r is 5 in Formula (5), the compoundin which q is 2 in Formula (6) and the compound in which t is 3 inFormula (10); the combination of the compound in which r is 5 in Formula(5), the compound in which q is 4 in Formula (6) and the compound inwhich t is 3 in Formula (10); and the combination of a compound in whichr is 5 and R is hydrogen in Formula (5) and a compound in which q is 2in Formula (6).

The properties of the compounds (5) and (7) and a synthetic methodthereof are the same as shown in the compounds (1) to (3) describedabove, and the properties of the compounds (6) and (8) and a syntheticmethod thereof are the same as shown in the compound (4) describedabove.

In the composition (II) of the invention, at least one compound selectedfrom the compounds (5) and at least one compound selected from thecompounds (6) as essential components are mixed, and the combination ofthe structural components, the composition ratio thereof or thetemperature in curing is changed, whereby obtained is a compositionexhibiting a cholesteric phase in a relatively broad temperature area inthe vicinity of room temperature.

In the composition (II) of the invention, a content of the compound (5)is usually approximately 2 to approximately 98 weight %, preferablyapproximately 50 to approximately 98 weight % and more preferablyapproximately 60 to approximately 95 weight %, and a content of thecompound (6) is usually approximately 2 to approximately 98 weight %,preferably approximately 2 to approximately 50 weight % and morepreferably approximately 5 to approximately 40 weight % each based onapproximately 100 weight % of the total of the essential components.

At least one selected from the compound (10) or at least one compoundselected from the compounds (7) and (8) which is contained in thecomposition (II) of the invention makes it possible to prevent thecomposition from being crystallized at room temperature, control areflected color at a specific temperature and develop a cholestericphase taking on reflected colors of red, orange, green and blue (purple)in a broader temperature region. Specifically, the compound (10) has ahigh effect in terms of preventing the composition from beingcrystallized at room temperature.

In the composition (II) of the invention, a content of the componentselected from the compound (10) is preferably approximately 10 toapproximately 60 weight %, more preferably approximately 20 toapproximately 50 weight % based on approximately 100 weight % of thetotal of the compounds (5), (6) and (10). Meanwhile, in the composition(II) of the invention, a content of the component selected from thecompounds (7) and (8) is preferably approximately 2 to approximately 30weight %, more preferably approximately 5 to approximately 20 weight %based on approximately 100 weight % of the total of the compounds (5) to(8).

Composition (III)

The composition (III) of the invention includes at least one compound(hereinafter referred to as the “first component”) selected from thecompounds (9), at least one compound (hereinafter referred to as the“second component”) selected from compounds the (8) and at least onecompound (hereinafter referred to as the “third component”) selectedfrom the group of multifunctional (meth)acrylates and (meth)acryloligomers.

The composition (III) of the invention may include a polymerizablecompound (other polymerizable compound) other than the first component,the second component and the third component each described above, anon-polymerizable component, an organic solvent and the like. Theproperties of the compound (9) and a synthetic method thereof are thesame as shown in the compounds (1) to (3).

In the composition (III) of the invention, the first component, thesecond component and the third component are mixed, and the combinationof the structural components, the composition ratio thereof or thetemperature in curing is changed, whereby obtained is a compositionexhibiting a cholesteric phase in a relatively broad temperature area inthe vicinity of room temperature.

In the composition (III) of the invention, a content of the firstcomponent is preferably approximately 50 to approximately 98 weight %,more preferably approximately 60 to approximately 98 weight %; a contentof the second component is preferably approximately 2 to approximately50 weight %, more preferably approximately 2 to approximately 40 weight%; and a content of the third component is preferably approximately 1 toapproximately 30 weight %, more preferably approximately 5 toapproximately 15 weight % each based on approximately 100 weight % ofthe total of the essential components.

Composition (IV)

The composition (IV) of the invention includes at least one compoundselected from compounds (5) and at least one compound selected fromcompounds (10). The composition (IV) of the invention may furtherinclude at least one compound selected from the group of the compound(4) in addition to the compounds (5) and (10). Further, the composition(IV) of the invention may include a polymerizable compound (the otherpolymerizable compound) other than the compounds (4), (5) and (10), anon-polymerizable component, an organic solvent and the like.

The preferred embodiment of the composition (IV) of the inventionincludes, for example, the combination of the compound in which r is 3in Formula (5) and the compound in which t is 3 in Formula (10); thecombination of the compound in which r is 5 in Formula (5) and thecompound in which t is 2 in Formula (10); the combination of thecompound in which r is 5 in Formula (5) and the compound in which t is 3in Formula (10); the combination of the compound in which r is 5 inFormula (5) and the compound in which t is 4 in Formula (10); thecombination of the compound in which r is 3 in Formula (5), and thecompound in which t is 3 in Formula (10) and the compound in which q is4 in Formula (4); and the combination of the compound in which r is 5 inFormula (5), the compound in which t is 3 and the compound in which q is2 in Formula (4).

In the composition (IV) of the invention, at least one selected from thecompounds (5) and at least one selected from the compounds (10) asessential components are mixed, and the combination of the structuralcomponents, the composition ratio thereof or the temperature in curingis changed, whereby obtained is a composition exhibiting a cholestericphase in a relatively broad temperature area in the vicinity of roomtemperature.

In the composition (IV) of the invention, a content of the compound (5)is usually approximately 2 to approximately 98 weight %, preferablyapproximately 50 to approximately 98 weight % and more preferablyapproximately 60 to approximately 95 weight %, and a content of thecompound (10) is usually approximately 2 to approximately 98 weight %,preferably approximately 2 to approximately 50 weight % and morepreferably approximately 5 to approximately 40 weight % each based onapproximately 100 weight % of the total of the essential components.

At least one compound selected from the compound (4) which is containedin the composition (IV) of the invention makes it possible to control areflected color at a specific temperature and develop a cholestericphase taking on reflected colors of red, orange, green and blue (purple)in a broader temperature region.

In the composition (IV) of the invention, a content of the componentselected from the compound (4) is preferably approximately 2 toapproximately 30 weight %, more preferably approximately 5 toapproximately 20 weight % based on approximately 100 weight % of thetotal of the compounds (4), (5) and (10).

Composition (V)

The composition (V) of the invention includes at least one compoundselected from compounds (4) and at least one compound selected fromcompounds (10). The composition (V) of the invention may include apolymerizable compound (the other polymerizable compound) other than thecompounds (4) and (10), a non-polymerizable component, an organicsolvent and the like.

The preferred embodiment of the composition (V) of the inventionincludes, for example, the combination of the compound in which q is 2in Formula (4) and the compound in which t is 2 in Formula (10); thecombination of the compound in which q is 2 in Formula (4) and thecompound in which t is 3 in Formula (10); the combination of thecompound in which q is 4 in Formula (4) and the compound in which t is 2in Formula (10); and the combination of the compound in which q is 4 inFormula (4) and the compound in which t is 3 in Formula (10).

In the composition (V) of the invention, at least one compound selectedfrom the compounds (4) and at least one compound selected from thecompounds (10) as essential components are mixed, and the combination ofthe structural components, the composition ratio thereof or thetemperature in curing is changed, whereby obtained is a compositionexhibiting a cholesteric phase in a relatively broad temperature area inthe vicinity of room temperature. Specifically, the compound (10) has ahigh effect in terms of preventing the composition from beingcrystallized at room temperature.

In the composition (V) of the invention, a content of the compound (4)is usually approximately 5 to approximately 70 weight %, preferablyapproximately 20 to approximately 60 weight %, and a content of thecompound (10) is usually approximately 30 to approximately 95 weight %,preferably 40 to approximately 80 weight % each based on approximately100 weight % of the total of the essential components.

At least one compound selected from the compound (4) which is containedin the composition (IV) of the invention makes it possible to control areflected color at a specific temperature and develop a cholestericphase taking on reflected colors of red, orange, green and blue (purple)in a broader temperature region.

In the composition (IV) of the invention, a content of the componentselected from the compound (4) is preferably approximately 2 toapproximately 30 weight %, more preferably approximately 5 toapproximately 20 weight % based on approximately 100 weight % of thetotal of the compounds (4), (5) and (10).

Other Polymerizable Compound

The polymerizable liquid crystal composition of the invention maycontain the other polymerizable compound as long as the effects of theinvention are not damaged. The other polymerizable compound may beliquid crystalline or non-liquid crystalline.

Publicly known polymerizable liquid crystal compounds can be used forthe other polymerizable compound having a liquid crystallinity andinclude the following compounds.

The other polymerizable compounds having a liquid crystallinity may beused alone or in combination of two or more kinds thereof. A content ofthe other polymerizable compounds having a liquid crystallinity in thecomposition of the invention is preferably approximately 2 toapproximately 30 weight %, more preferably approximately 2 toapproximately 15 weight % based on approximately 100 weight % of thetotal of the essential components. A content of the other polymerizablecompounds having a liquid crystallinity which falls in the rangedescribed above makes it possible to control temperature at which acholesteric phase is developed to room temperature or higher.

A system used as a binder for a coating material can be used for theother polymerizable compound having a non-liquid crystallinity. Theabove binder includes monomer agents, polymer binders and mixturesthereof.

The monomer agents are compounds having a polymerizable group(hereinafter referred to as a “cross-linkable group”). Thecross-linkable group includes, for example, acryl, methacryl,α-halogenated acryl, vinyl, vinyl ether, oxirane, oxetane, cyanate andisocyanate groups. Among them, acryl, methacryl and vinyl ether groupsare preferred. The monomer agents may be compounds having onecross-linkable group or compounds having plural cross-linkable groups.

The monomer agent having one cross-linkable group includes, for example,methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate,2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, laurylmethacrylate, styrene, acrylonitrile, acrylamide, N-methylolacrylamide,β-hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid,methacrylic acid, itaconic acid, maleic anhydride and aginidinylmethacrylate.

The monomer agent having two cross-linkable groups includes, forexample, diacrylates, divinyl ethers and dimethacrylates of propanediol,butanediol, hexanediol, ethylene glycol, diethylene glycol, triethyleneglycol or tetrapropylene glycol.

The monomer agent having three cross-linkable groups includes, forexample, triacrylates, trivinyl ethers and trimethacrylates oftrimethylolpropane, ethoxylated trimethylolpropane having approximately1 to approximately 20 ethylene oxide structural units, propoxylatedtrimethylolpropane having approximately 1 to approximately 20 propyleneoxide structural units or ethoxylated.propoxylated trimethylolpropanehaving approximately 1 to approximately 20 ethylene oxide structuralunits and propylene oxide structural units in total; and triacrylates,trivinyl ethers and trimethacrylates of ethoxylated glycerin havingapproximately 1 to approximately 20 ethylene oxide structural units orpropoxylated glycerin having approximately 1 to approximately 20propylene oxide structural units, such as glycerin epoxy triacrylate.

The monomer agent having four cross-linkable groups includes, forexample, pentaerythritol tetraacrylate, and tetraacrylates, tetravinylethers and tetramethacrylates of ethoxylated bis-tetramethylolpropanehaving approximately 1 to approximately 20 ethylene oxide structuralunits, propoxylated bis-trimethylolpropane having approximately 1 toapproximately 20 propylene oxide structural units orethoxylated.propoxylated bistrimethylolpropane having approximately 1 toapproximately 20 ethylene oxide structural units and propylene oxidestructural units in total.

The monomer agent having five cross-linkable groups includes, forexample, dipentaerythritol pentaacrylate, ethoxylated dipentaerythritolpentaacrylate having approximately 1 to approximately 20 ethylene oxidestructural units, propoxylated dipentaerythritol pentaacrylate havingapproximately 1 to approximately 20 propylene oxide structural units,and pentaacrylates, pentavinyl ethers and pentatrimethacrylates ofethoxylated.propoxylated dipentaerythritol having approximately 1 toapproximately 20 ethylene oxide structural units and propylene oxidestructural units in total.

The polymer binder described above includes (meth)acryl oligomers,urethane acrylate oligomers, epoxy oligomers and the like.

The other polymerizable compounds having a non-liquid crystallinity aremore preferably monofunctional (meth)acrylate monomers, multifunctional(meth)acrylate monomers and (meth)acryl oligomers. The multifunctional(meth)acrylate monomers and the (meth)acryl oligomers can be used as thethird component in the composition (III) of the invention, and in thiscase, they are not included in the other polymerizable compounds.

The other polymerizable compounds having a non-liquid crystallinity maybe used alone or in combination of two or more kinds thereof. In thecomposition of the invention, a content of the other polymerizablecompounds having a non-liquid crystallinity is different depending onthe structure of the polymerizable liquid crystal compound and thecomposition ratio thereof, and it is preferably approximately 40 weight% or less, more preferably approximately 30 weight % or less and furtherpreferably approximately 20 weight % or less based on approximately 100weight % of the total of the essential components. A content of theother polymerizable compounds having a non-liquid crystallinity whichfalls in the range described above maintains a liquid crystal phase ofthe composition without bringing about phase separation.

Non-Polymerizable Component

The polymerizable liquid crystal composition of the invention may beblended with a non-polymerizable component as long as the effects of theinvention are not damaged. The non-polymerizable component may be liquidcrystalline or non-liquid crystalline and includes, for example,non-polymerizable liquid crystal compounds, extender pigments,colorants, dispersants, polymerization initiators, sensitizers,polymerization inhibitors, oxygen inhibitors, antioxidants, UVabsorbers, surfactants, adhesive aids, adhesion accelerators, storagestabilizers, defoamers, flocculation preventives and the like.

The non-polymerizable liquid crystal compounds are described inLiqCryst, LCI Publisher GmbH, Hamburg, Germany which is a data base forliquid crystal compounds. The non-polymerizable liquid crystal compoundsmay be used alone or in combination of two or more kinds thereof.

The extender pigments which are generally added to coating materialsinclude, for example, barium sulfate, barium carbonate, calciumcarbonate, magnesium carbonate, silica, titanium oxide, mica, sericite,talc and the like. The above extender pigments may be used alone or incombination of two or more kinds thereof.

The colorants include organic pigments which are generally added toresins, and they include, to be more specific, soluble azo, insolubleazo, polyazo, phthalocyanine, anthraquinone, thioindigo, perylene,perinone, dioxazine, quinacridone, isoindolinone, quinophthalone,diketopyrrolopyrrole, anthraquinone, perinone, quinophthalone, azo,carbon black and the like. Among them, soluble azo, insoluble azo,polyazo, phthalocyanine, quinacridone, dioxazine, quinophthalone andcarbon black are preferred.

Low molecular or high molecular dispersants which are conventionallyused can be used for the dispersants. The low molecular dispersantsinclude, for example, stearic acid and the like, and the high moleculardispersants include polyurethanes having a sulfonate group, a phosphategroup, a phosphonate group or a carboxyl group, carboxylgroup—containing vinyl chloride polymers, polyiminepolyesters, polyetheracrylate and the like.

The polymerizable liquid crystal composition of the invention maycontain a conventional photopolymerization initiator when subjected tooptical radical polymerization. The initiator has a maximum absorptionwavelength in an ultraviolet, near ultraviolet or visible light region,and a polymer may be produced by irradiating the composition therewithat room temperature or heating at the same time as irradiation.

The photopolymerization initiators include, for example,2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651™),1-hydroxycyclohexyl phenyl ketone (Irgacure 184™),2-hydroxy-2-methyl-1-phenyl-propane-1-one (Dalocure 1173™), Irgacure500™, Irgacure 1000™,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one(Irgacure 295™),2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (Irgacure907™), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1(Irgacure 369™),2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone(Irgacure 379™), Irgacure 1800™, Irgacure 1850™, Dalocure 4265™,Dalocure 1116™, Irgacure 784™,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819™),Irgacure 784™, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)](Irgacure OXE01™),ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) (Irgacure OXE02™),2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propane-1-one(Irgacure 127™) and Irgacure 754™ which are products manufactured byCiba Specialty Chemicals K. K.

The photopolymerization initiators include, in addition to the abovecompounds, acetophenone, benzophenone,4,4′-bisdimethylaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone,benzil, benzoyl, benzoin ethyl ether, benzoin butyl ether, benzoinisobutyl ether, azoisobutylnitrile, 2-chlorothioxanthone,2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone,2-isopropylthioxanthone, 2,4-diethylthioxanthone, methylphenylglyoxylate, 3,3′,4,4-tetra(t-butylperoxycarbonyl)benzophenone, ethylp-dimethylaminobenzoate, 2-dimethylaminoeklbenzoate, isoamylp-dimethylaminobenzoate, N,N-dimethylaminoethyl methacrylate, abenzophenone/methyltriethanolamine mixture, a 2,2-diethylxanthone/methylp-dimethylaminobenzoate mixture,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, benzyldimethyl ketal, acetophenone dimethyl ketal,2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone,1,1-dichloroacetophenone, diethoxyacetophenone,2-hydroxy-2-methyl-phenylpropane-1-one, 1-hydroxycyclohexyl phenylketone, 2-ethylanthraquinone, 2-tertiary butylanthraquinone,2-chloroanthraquinone, 2-aminoanthraquinone, benzophenone,4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone,2,4,6-trimethylbenzoyldiphenylphosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like.

The polymerization initiators are preferably used in an amount fallingin a range of approximately 0.01 to approximately 10 parts by weight perapproximately 100 parts by weight of the total amount of the compoundshaving an ethylenically unsaturated bond which is radicallypolymerizable.

The composition of the invention may contain a sensitizer in addition tothe polymerization initiator. The sensitizer includes, for example,coumarins having substituents at a 3-position and/or a 7-position,flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthenes,thioxanthenes, porphyrins, acridines and the like.

The composition of the invention may contain a surfactant such as anonionic surfactant, a cationic surfactant, an anionic surfactant andthe like in order to enhance a coating property on an objectivesubstrate. It includes, to be specific: nonionic surfactants includingpolyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether,polyoxyethylene stearyl ether and polyoxyethylene oleyl ether,polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl etherand polyoxyethylene nonylphenyl ether and polyethylene glycol dialkylesters such as polyethylene glycol dilaurate and polyethylene glycoldistearate; fluorine base surfactants such as Eftop EF301™, Eftop EF303™and Eftop EF352™ (manufactured by Shin Akita Chemical Co., Ltd.),Megafac F171™, Megafac F172™ and Megafac F173™ (manufactured byDainippon Ink & Chemicals Inc.), Fluorad FC430™ and Fluorad FC431™(manufactured by Sumitomo 3M Limited) and Asahi Guard AG710™, SurflonS-382™, Surflon SC-101™, Surflon SC-102™, Surflon SC-103™, SurflonSC-104™, Surflon SC-105™ and Surflon SC-106™ (manufactured by AsahiGlass Co., Ltd.); Organosiloxane Polymer KP341™ (manufactured byShin-Etsu Chemical Co., Ltd.) and acrylic acid base or methacrylic acidbase (co)polymer Polyflow No. 57™ and Polyflow No. 95™ (manufactured byKyoeisha Chemical Co., Ltd.). The surfactants are used in an amount ofapproximately 5 parts by weight or less based on the polymer.

The polymerizable liquid crystal composition of the invention maycontain a close adhesiveness-accelerating agent in order to improve aclose adhesiveness on a substrate which is an object for applying. Theclose adhesiveness-accelerating agent includes, for example,vinyltrimethoxysilane, vinyltriethoxysilane,vinyltris(2-methoxyethoxy)silane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyldimethoxysilane,3-glycidoxypropylmethyldimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltimethoxysilane,3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilaneand the like.

The antioxidants include, for example,2,2-methylenebis(4-methyl-6-t-butylphenol),2,6-di-t-butyl-4-methylphenol (BHT) and the like.

The UV absorbers include, for example,2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,alkoxybenzophenones and the like.

The flocculation preventives include, for example, sodium polyacrylateand the like.

Organic Solvent

The polymerizable liquid crystal composition of the invention maycontain an organic solvent in order to dilute the composition or enhancethe coating property. The organic solvent includes linear or branchedesters, particularly acetic esters, cyclic ethers, cyclic esters,alcohols, lactone, aliphatic hydrocarbons, aromatic hydrocarbons,toluene, xylene, cyclohexane, ketones, amides, N-alkylpyrrolidones,tetrahydrofuran, dioxane, methyl ethyl ketone and the like. The organicsolvents may be used alone or in combination of two or more kindsthereof.

Polymer

The polymer according to the invention is obtained by polymerizing thepolymerizable liquid crystal composition of the invention, and acholesteric liquid crystal phase of the composition is fixed to reflectlight of a wavelength according to the desired colors and the purposes.The polymerization reaction of the composition may be either thermalpolymerization by heating or photopolymerization by irradiation withlight, and it may be carried out by a method obtained by combining both.

The kind of preferred light used for photopolymerization is a UV ray, avisible light and an infrared ray, and an electromagnetic wave such asan electron beam and an X-ray may be used. Usually, a UV ray or avisible light is used. The range of the wavelength is approximately 150to approximately 500 nm, preferably approximately 250 to approximately450 nm and particularly preferably approximately 300 to approximately400 nm. The light source includes a low pressure mercury lamp (abactericidal lamp, a fluorescent chemical lamp and a black light), ahigh pressure discharge lamp (a high pressure mercury lamp and a metalhalide lamp) and a short arc discharge lamp (an extra-high pressuremercury lamp, a xenon lamp and a mercury xenon lamp), and an extra-highpressure mercury lamp is preferred.

Light coming from the light source may be irradiated on the compositionas it is, or a specific wavelength (or a specific wavelength region)which is selected through a filter may be irradiated on the composition.The irradiation energy density falls in the range of approximately 2 toapproximately 5,000 mJ/cm², preferably approximately 10 to approximately3,000 mJ/cm² and particularly preferably approximately 100 toapproximately 2,000 mJ/cm². The illuminance falls in a range ofapproximately 0.1 to approximately 5000 mW/cm², preferably approximately1 to approximately 2,000 mW/cm².

The polymer of the invention can be obtained by applying thepolymerizable liquid crystal composition of the invention directly onthe surface of a substrate which is an object and then polymerizing it.Accordingly, multistage operation in which a cholesteric polymer iscrushed into a flake form or in which cholesteric liquid crystal ismicroencapsulated, mixed again with a solvent and the like and appliedon an object does not have to be carried out. The form of the polymershall not specifically be restricted and may be a film form, a plate andthe like, and the polymer may be molded.

In the composition of the invention, a wavelength region of lightreflected by a cholesteric phase can be controlled in a wide range ofred, green, blue and purple by changing the combination of thestructural components, the composition ratio thereof and a curingtemperature of the composition. Accordingly, the polymer reflectinglight of a wavelength according to the desired colors and the purposescan be obtained without strictly controlling the temperature conditionin curing.

Uses

Uses for the polymerizable liquid crystal composition, for example,cosmetic ingredients, printing inks, UV curing type printing inks andthe like.

Uses for the polymer of the invention include conventional films,cosmetic ingredients, color materials, for example, liquid crystalpigments, coating materials, spray inks, print inks and the like.Further, it can be used as well for cosmetics (for example, lip rouge,lip cream, lip gloss, eye shadow, eye liner, mascara, rouge, liquidfoundation and nail colors), printed matters for preventing counterfeit,ornamental articles, toys or optical films such as polarizing plates,compensation plates and color filters in optical elements such as liquidcrystal displays and holographic devices.

The objects, features, advantages and ideas of the invention will beapparent to those skilled in the art from the description provided inthe specification, and the invention will be readily practicable bythose skilled in the art on the basis of the description appearingherein. The Description of the Preferred Embodiments and the Exampleswhich show preferred modes for practicing the invention are included forthe purpose of illustration and explanation, and are not intended tolimit the scope of the claims. It will be apparent to those skilled inthe art that various modifications may be made in how the invention ispracticed based on described aspects in the specification withoutdeparting from the spirit and scope of the invention disclosed herein.Thus, it is intended that the invention covers the modifications andvariations of this invention that come within the scope of any claimsand their equivalents.

EXAMPLES

The present invention shall more specifically be explained below withreference to examples, but the present invention shall not be restrictedto these examples.

Synthetic Example 1

A compound (compound in which m is 5 in Formula (1)) represented by thefollowing formula was synthesized in the following manner.

First Step:

Sodium hydroxide 173 g was dissolved in 867 g of water, and then 150 gof ε-caprolactone which was a raw material was added dropwise theretoand stirred at room temperature for 5 hours. After neutralized with 6Nhydrochloric acid, the solution was extracted with ethyl acetate, andthen the organic layer was washed with water. The organic layer wasdried on anhydrous magnesium sulfate, and then the solvent was distilledoff under reduced pressure. The residue was recrystallized from a mixedsolvent of tetrahydrofuran (THF) and heptane to obtain 106.47 g of1-hydroxyhexanoic acid. ¹H-NMR (CDCl₃; δ ppm): 3.68 (t, 2H), 2.38 (t,2H), 1.57 to 1.72 (m, 4H), 1.39 to 1.47 (m, 2H).

Second Step:

Acrylic chloride 80 g was dropwise added to a mixture of 1067 g of1-hydroxyhexanoic acid, 109 g of N,N-dimethylaniline, 0.9 g of BHT and1,000 mL of dioxane at room temperature, and subsequently the solutionwas stirred at 60° C. for 2 hours. The reaction mixture was poured intoice and water, and ethyl acetate was added thereto and stirred. Afterseparating the liquid, the ethyl acetate layer was washed in the orderof 1N hydrochloric acid, a saturated sodium carbonate aqueous solutionand water and dried on anhydrous magnesium sulfate, and then the solventwas distilled off under reduced pressure to obtain a concentrate (148.56g) of 6-acryloyloxyhexanoic acid. ¹H-NMR (CDCl₃; δ ppm): 6.38 (dd, 1H),6.14 (dd, 1H), 5.83 (dd, 1H), 4.16 (t, 2H), 2.38 (t, 2H), 1.64 to 1.73(m, 4H), 1.40 to 1.47 (m, 2H).

Third Step:

A dichloromethane 80 mL solution of 19 g ofN,N′-dicyclohexylcarbodiimide was dropwise added to a mixture of 70 g of6-acryloyloxyhexanoic acid, 121 g of cholesterol, 19 g of4-dimethylaminopyridine and 1,500 mL of dichloromethane under coolingwith ice. The solution was stirred at room temperature for 18 hours, andinsoluble matters were removed by filtering. Water was added to thefiltrate, and the organic layer was washed in the order of 1Nhydrochloric acid, a 2N sodium hydroxide aqueous solution and water anddried on anhydrous magnesium sulfate. Then, the solvent was distilledoff under reduced pressure. The residue was filtered through celite, andthe filtrate was separated by silica gel chromatography (heptane/ethylacetate=9/1) and then recrystallized from a mixed solvent of diethylether and ethanol to obtain 100.35 g of 6-acryloyloxyhexanoic acidcholesterol ester. Melting point: 45.3 to 45.8° C. ¹H-NMR (CDCl₃; δppm): 6.41 (dd, 1H), 6.12 (dd, 1H), 5.37 (d, 1H), 4.59 to 4.63 (m, 1H),4.15 (t, 2H), 2.29 (t, 2H), 0.6 to 1.96 (m, 47H).

Among compounds used in the following examples, the compoundsrepresented by Formulas (1) to (3), (5), (7) and (9) were synthesized bythe same method as described above.

Example A1

Prepared was a composition comprising 91% by weight of the compound(compound in which m is 5 in Formula (1)) obtained in Synthetic Example1 and 9% by weight of a compound in which n is 3 and R is hydrogen inFormula (2). The composition showed selective reflection of a greencolor at 22° C. The composition (1 g) was mixed with 0.01 g of Irgacure651™ (manufactured by Ciba Specialty Chemicals K. K.) as apolymerization initiator, and the mixture was dissolved in toluene andapplied on a glass substrate. After applied, the substrate was subjectedto heat treatment for 3 minutes in an oven set to 120° C. to remove thesolvent, whereby a coating film was formed. Then, the coating film wasirradiated with a UV ray for 30 seconds by means of a high pressuremercury lamp (70 mW/cm²). The above composition was polymerized byirradiation and showed the same selective reflection of a green color asin applying the composition before polymerized on a glass substrate. Theresults thereof are shown in Table 1.

Examples A2 to A8

Polymers were produced in the same manner as in Example A1 to observereflected colors, except that compositions having formulations shown inTable 1 were prepared. The results thereof are shown in Table 1.

TABLE 1 Compound Compound (1) (2) m = 5 n = 3, R═H Reflected Color % byweight % by weight 22° C. 40° C. Example A1 91 9 Green Example A2 83 17Green Example A3 80 20 Green Example A4 70 30 Greenish yellow Example A567 33 Orange + green Viridian Example A6 62 38 Orange Green (vermilion)Example A7 57 43 Sanguine Greenish yellow Example A8 50 50 Ruby redGreenish yellow

Examples B1 to B4

Polymers were produced in the same manner as in Example A1 to observereflected colors, except that compositions having formulations shown inTable 2 were prepared. The results thereof are shown in Table 2.

Example C1

A polymer was produced in the same manner as in Example A1 to observe areflected color, except that a composition having a formulation shown inTable 2 was prepared. The results thereof are shown in Table 2.

TABLE 2 Compound (2) Compound (4) Compound (1) n = 3 q = 2 m = 5 m = 10R═H R═H Reflected Color % by weight % by weight % by weight % by weight22° C. 40° C. Ex. B1 44 11 44 — Red Green Ex. B2 40 20 40 — OrangeViridian Ex. B3 36 27 36 — Green Blue Ex. B4 33 33 33 — Blue Blue Ex. C144 — 44 12 Transparent (red)

Examples D1 to D5

Polymers were produced in the same manner as in Example A1 to observereflected colors, except that compositions shown in Table 3 wereprepared. The results thereof are shown in Table 3.

TABLE 3 Compound (5) r = 5 Compound (6) R═ H q = 2 Reflected Color % byweight % by weight 22° C. 40° C. Ex. D1 5 95 Red to orange Ex. D2 10 90Greenish yellow Ex. D3 20 80 Green Ex. D4 30 70 Blue Blue Ex. D5 40 60Blue Blue

Reference Example E1 and Example E2

Polymers were produced in the same manner as in Example A1 to observereflected colors, except that compositions shown in Table 4 wereprepared. The results thereof are shown in Table 4. Trimethylolpropanetriacrylate was used as the third component.

TABLE 4 First Component Second Component Compound (9) Compound (8) Thirds = 5, R═H q = 2 Component Reflected Color % by weight % by weight % byweight 25° C. 35° C. Reference 60 40 — Colorless Red Example E1 ExampleE2 55 36 9 Red Red

Examples F1 to F13

Polymers were produced in the same manner as in Example A1 to observereflected colors, except that compositions shown in Table 5 wereprepared. The results thereof are shown in Table 5.

TABLE 5 Compound (5) Compound (4) Compound (10) r = 3, R═H r = 5, R═H q= 2, R═H q = 4, R═H t = 3, R═H Reflected Color % by weight % by weight %by weight % by weight % by weight 24° C. 40° C. Ex. F1 33 33 33 Orangeto Green greenish yellow Ex. F2 38 38 24 Red Red Ex. F3 33 33 33 Orangeto Green greenish yellow Ex. F4 38 38 24 Vermilion Greenish yellow Ex.F5 43 43 14 Red Green Ex. F6 44 44 12 Red Greenish yellow Ex. F7 33 3333 Blue Blue Ex. F8 25 25 50 Orange to Greenish greenish yellow yellowEx. F9 25 50 25 Red Red Ex. F10 25 50 25 Green Green Ex. F11 50 50 BlueBlue Ex. F12 20 40 40 Red Orange Ex. F13 50 50 Blue Blue

Comparative Examples 1 to 11

Results obtained in examples described in JP S59-109505 A/1984 shall beshown as comparative examples in Table 6.

TABLE 6 Compound (2) Compound (4) Compound (1) n = 3 n = 3 Compound (3)q = 2 q = 6 q = 2 Reflected m = 5 m = 10 R═H R═CH₃ p = 5 p = 10 R═H R═HR═CH₃ Color Remarks Comp. — 50 50 — — — — — — Purple to 68 to −15° C.Ex. 1 orange red Comp. — — — — — 50 50 — — Green to 475 to −15° C. Ex. 2orange Comp. — — 50 — — 50 — — — Purple to 50 to −5° C. Ex. 3 red Comp.— — — 50 — 50 — — — Bluish purple to 40 to −5° C. Ex. 4 red Comp. — — —50 50 — — — — Green to 45 to 30° C. Ex. 5 red Comp. — — — — — 50 50 — —Orange green 32 to 0° C. Ex. 6 to red Comp. — — 30 — 40 20 — — — Purpleto 16 to 6° C. Ex. 7 orange Comp. — — — — — 50 — — 50 585 nm (25.5° C.)Ex. 8 Comp. 75 — — — — — 25 — — 563 nm (25.5° C.) Ex. 9 Comp. 50 — — — —— 50 — — 950 nm (24.5° C.) Ex. 10 Comp. 50 — — — — — — 50 — 1260 nm(25.5° C.) Ex. 11

As shown in Table 6, temperature dependency of reflected colors in thecholesteric reflection bands of the compositions comprising the samemonofunctional acrylates as the compounds of the present invention isshown in Comparative Examples 1 to 7. It can be found that particularlyin Comparative Example 1, a cholesteric phase taking on reflected colorsof red to purple is maintained in a broad temperature range of −15 to68° C.

However, the reflected colors shown in the vicinity of room temperatureare limited. That is, a film having an inherent reflected color whichwas produced by using the composition prepared in Comparative Example 1was prepared as well, and the temperature of the composition was changedat the intervals of 10° C., 18° C., 23° C. and 32° C. to control thereflected colors. Thus, it is not described in JP S59-109505 A/1984 thata polymer taking on the specific reflected colors of red, green and blueat a fixed temperature of room temperature is obtained as is the casewith the invention.

Also, in other Comparative Examples 2, 3, 4 and 6, red and orange colorswere shown at a relatively low temperature, that is, room temperature orlower. In Comparative Examples 5 and 7, a temperature range in acholesteric phase area fallen in a range of 10 to 15° C. It can not befound that stable reflected colors of red to blue (purple) are shown atroom temperature in all the above comparative examples. The invention ischaracterized by providing a polymerizable liquid crystal compositionshowing a reflected color in a broad range of red to blue (purple) atsome fixed room temperature by changing the constitution of thecomposition and providing a polymer thereof.

In Comparative Example 10, the composition having a component ratio of1:1 didn't take on a reflected color in the vicinity of roomtemperature. Compositions in which a composition ratio was changed as isthe case with Example 9 showed inherent reflected colors at roomtemperature. However, polymerizable liquid crystal compositions showingreflected colors in a broad range of red to blue (purple) in thevicinity of room temperature are not obtained from only the above twocomponent system.

Although the invention has been described and illustrated with a certaindegree of particularity, it is understood that the disclosure has beenmade only by way of example, and that numerous changes in the conditionsand order of steps can be resorted to by those skilled in the artwithout departing from the spirit and scope of the invention.

1. A polymerizable liquid crystal composition comprising at least onecompound selected from the group of compounds represented by Formula (5)and at least one compound selected from the group of compoundsrepresented by Formula (6):

wherein r is an integer of 3 to 9, and R is hydrogen or methyl; and

wherein q is 2, 4 or
 6. 2. The polymerizable liquid crystal compositionof claim 1, further comprising at least one compound selected from thegroup of compounds represented by Formula (10):

wherein t is 2, 3 or 4, and R is hydrogen or methyl.
 3. Thepolymerizable liquid crystal composition of claim 2, comprising thecompound in which r is 5 in Formula (5), the compound in which q is 2 inFormula (6) and the compound in which t is 2 in Formula (10).
 4. Thepolymerizable liquid crystal composition of claim 2, comprising thecompound in which r is 5 in Formula (5), the compound in which q is 4 inFormula (6) and the compound in which t is 2 in Formula (10).
 5. Thepolymerizable liquid crystal composition of claim 2, comprising thecompound in which r is 5 in Formula (5), the compound in which q is 2 inFormula (6) and the compound in which t is 3 in Formula (10).
 6. Thepolymerizable liquid crystal composition of claim 2, comprising thecompound in which r is 5 in Formula (5), the compound in which q is 4 inFormula (6) and the compound in which t is 3 in Formula (10).
 7. Thepolymerizable liquid crystal composition of claim 1, further comprisingat least one compound selected from the group of compounds representedby Formulas (7) and (8):

wherein R is hydrogen or methyl; and

wherein q is 2, 4 or
 6. 8. The polymerizable liquid crystal compositionof claim 1, comprising the compound in which r is 5 and R is hydrogen inFormula (5) and the compound in which q is 2 in Formula (6).
 9. Apolymerizable liquid crystal composition comprising at least onecompound selected from the group of compounds represented by Formula(9),

wherein s is an integer of 3 to 10, and R is hydrogen or methyl; atleast one compound selected from the group of compounds represented byFormula (8)

wherein q is 2, 4 or 6; and at least one compound selected from thegroup of multifunctional (meth)acryl monomers and (meth)acryl oligomers.10. A polymerizable liquid crystal composition comprising at least onecompound selected from the group of compounds represented by Formula (5)and at least one compound selected from the group of compoundsrepresented by Formula (10):

wherein r is an integer of 3 to 9, and R is hydrogen or methyl; and

wherein t is 2, 3 or 4, and R is hydrogen or methyl.
 11. Thepolymerizable liquid crystal composition of claim 10, comprising thecompound in which r is 3 in Formula (5) and the compound in which t is 3in Formula (10).
 12. The polymerizable liquid crystal composition ofclaim 10, comprising the compound in which r is 5 in Formula (5) and thecompound in which t is 2 in Formula (10).
 13. The polymerizable liquidcrystal composition of claim 10, comprising the compound in which r is 5in Formula (5) and the compound in which t is 3 in Formula (10).
 14. Thepolymerizable liquid crystal composition of claim 10, comprising thecompound in which r is 5 in Formula (5) and the compound in which t is 4in Formula (10).
 15. The polymerizable liquid crystal composition ofclaim 10, further comprising at least one compound selected from thegroup of compounds represented by Formula (4):

wherein q is 2, 4 or 6, and R is hydrogen or methyl.
 16. Thepolymerizable liquid crystal composition of claim 15, comprising thecompound in which r is 3 in Formula (5), the compound in which t is 3 inFormula (10) and the compound in which q is 4 in Formula (4).
 17. Thepolymerizable liquid crystal composition of claim 15, comprising thecompound in which r is 5 in Formula (5), the compound in which t is 3 inFormula (10) and the compound in which q is 2 in Formula (4).
 18. Apolymerizable liquid crystal composition comprising at least onecompound selected from the group of compounds represented by Formula (4)and at least one compound selected from the group of compoundsrepresented by Formula (10):

wherein q is 2, 4 or 6, and R is hydrogen or methyl; and

wherein t is 2, 3 or 4, and R is hydrogen or methyl.
 19. Thepolymerizable liquid crystal composition of claim 18, comprising thecompound in which q is 2 in Formula (4) and the compound in which t is 2in Formula (10).
 20. The polymerizable liquid crystal composition ofclaim 18, comprising the compound in which q is 2 in Formula (4) and thecompound in which t is 3 in Formula (10).
 21. The polymerizable liquidcrystal composition of claim 18, comprising the compound in which q is 4in Formula (4) and the compound in which t is 2 in Formula (10).
 22. Thepolymerizable liquid crystal composition of claim 18, comprising thecompound in which q is 4 in Formula (4) and the compound in which t is 3in Formula (10).